4-[[tert-butyl(dimethyl)silyl]oxymethyl]benzaldehyde

Conditions: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-(t-Butyldimethylsilyloxymethyl)benzaldehyde (Synthesis (1995), 12, 1529-33) (6.65 gm, 26 mmol) was dissolved in dry tetrahydrofuran (50 mL) and the solution cooled to −40° C. Benzyl magnesium chloride in diethyl ether (1 M, 35 mL, 35 mmol) was added slowly. The reaction was allowed to warm to 0° C. over three hours. The reaction was then quenched by the addition of ammonium chloride (2.3 gm, 43 mmol) in water (60 mL). The product was extracted into diethyl ether, washed with NaHCO3 solution, dried (over Na2SO4), and filtered. The solution was evaporated to give 1-[4-t-butyldimethylsilyloxymethyl)-phenyl]-2-phenylethanol as an oil which was used as is. 1H-NMR (500 MHz, CDCl3): δ 7.19-7.34 (9H, m), 4.90 (1H, dd, J=4.9, 8.3 Hz), 4.75 (2H, s), 2.98-3.07 (2H, dt), 0.95 (6H, s), 0.11 (9H, s). to warm to 0° C. over three hours The product was extracted into diethyl ether washed with NaHCO3 solution dried (over Na2SO4) filtered The solution was evaporated

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of oxalyichloride (1.6 ml) in dry dichloromethane (37 ml) was cooled to -70° C. under N2. Dry dimethylsulfoxide (2.5 ml) in dichloromethane (10 ml) and a solution of 4-(tert-butyldimethylsilyloxymethyl)benzylalcohol (24) (3.94 g, 15.6 mmol) in dichloromethane (20 ml) were added carefully. The reaction mixture was stirred at -70° C. for 1 h. trimethylamine (12 ml) was then added. The reaction mixture was allowed to warm up no 0° C. Saturated aqueous sodium bicarbonate (50 ml) was added, the organic layer was separated and the aqueous layer was extracted with dichloromethane (4×50 ml). The combined organic extracts were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by column chromatography over silica (dichloromethane/hexane; 4:1) to yield 4-butyldimethylsilyloxymethyl)benzaldehyde (25) 3.21 g, 82%); νmax /cm-1 2020s, 2850s, 2730w, 1700s, 1090s; δH (CDCl3) 0.11 (6H, s, SiCH3), 0.94 (9 H, s, tert-butyl), 4.80 (2 H, s, CH2O), 7.47 and 7.84 (4 H, AA'BB', PhH) and 9.98 (1 H, s, CHO); (CDCl3) -5.3, 18.4, 25.9, 64.4, 126.2, 129.8, 135.3, 148.6 and 192.0; m/z 251.1467 M+ +H). was then added the organic layer was separated the aqueous layer was extracted with dichloromethane (4×50 ml) The combined organic extracts were dried over anhydrous sodium sulfate filtered concentrated in vacuo The residue was purified by column chromatography over silica (dichloromethane/hexane; 4:1)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of oxalyichloride (1.6 ml) in dry dichloromethane (37 ml) was cooled to -70° C. under N2. Dry dimethylsulfoxide (2.5 ml) in dichloromethane (10 ml) and a solution of 4-(tert-butyldimethylsilyloxymethyl)benzylalcohol (24) (3.94 g, 15.6 mmol) in dichloromethane (20 ml) were added carefully. The reaction mixture was stirred at -70° C. for 1 h. trimethylamine (12 ml) was then added. The reaction mixture was allowed to warm up no 0° C. Saturated aqueous sodium bicarbonate (50 ml) was added, the organic layer was separated and the aqueous layer was extracted with dichloromethane (4×50 ml). The combined organic extracts were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by column chromatography over silica (dichloromethane/hexane; 4:1) to yield 4-butyldimethylsilyloxymethyl)benzaldehyde (25) 3.21 g, 82%); νmax /cm-1 2020s, 2850s, 2730w, 1700s, 1090s; δH (CDCl3) 0.11 (6H, s, SiCH3), 0.94 (9 H, s, tert-butyl), 4.80 (2 H, s, CH2O), 7.47 and 7.84 (4 H, AA'BB', PhH) and 9.98 (1 H, s, CHO); (CDCl3) -5.3, 18.4, 25.9, 64.4, 126.2, 129.8, 135.3, 148.6 and 192.0; m/z 251.1467 M+ +H). was then added the organic layer was separated the aqueous layer was extracted with dichloromethane (4×50 ml) The combined organic extracts were dried over anhydrous sodium sulfate filtered concentrated in vacuo The residue was purified by column chromatography over silica (dichloromethane/hexane; 4:1)

Conditions: temp:-40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-(t-Butyldimethylsilyloxymethyl)benzaldehyde (Synthesis (1995), 12, 1529-33) (6.65 gm, 26 mmol) was dissolved in dry tetrahydrofuran (50 mL) and the solution cooled to −40° C. Benzyl magnesium chloride in diethyl ether (1 M, 35 mL, 35 mmol) was added slowly. The reaction was allowed to warm to 0° C. over three hours. The reaction was then quenched by the addition of ammonium chloride (2.3 gm, 43 mmol) in water (60 mL). The product was extracted into diethyl ether, washed with NaHCO3 solution, dried (over Na2SO4), and filtered. The solution was evaporated to give 1-[4-t-butyldimethylsilyloxymethyl)-phenyl]-2-phenylethanol as an oil which was used as is. 1H-NMR (500 MHz, CDCl3): δ 7.19-7.34 (9H, m), 4.90 (1H, dd, J=4.9, 8.3 Hz), 4.75 (2H, s), 2.98-3.07 (2H, dt), 0.95 (6H, s), 0.11 (9H, s). to warm to 0° C. over three hours The product was extracted into diethyl ether washed with NaHCO3 solution dried (over Na2SO4) filtered The solution was evaporated